Key Laboratory of Analytical Chemistry for Biology and Medicine (Ministry of Education), Department of Chemistry, Wuhan University, Wuhan 430072, China.
J Chromatogr A. 2013 Oct 4;1310:21-30. doi: 10.1016/j.chroma.2013.08.047. Epub 2013 Aug 20.
In this work, three kinds of metal-organic frameworks (MOFs), MOF-5, MOF-199 and IRMOF-3, were introduced in stir bar sorptive extraction (SBSE) and novel polydimethylsiloxane (PDMS)/MOFs (including PDMS/MOF-5, PDMS/MOF-199 and PDMS/IRMOF-3) coated stir bars were prepared by sol-gel technique. These PDMS/MOFs coatings were characterized and critically compared for the extraction of seven target estrogens (17-β-estradiol, dienestrol, diethylstilbestrol, estrone, 4-t-octylphenol, bisphenol-A and 17α-ethynylestradiol) by SBSE, and the results showed that PDMS/IRMOF-3 exhibited highest extraction efficiency. Based on the above facts, a novel method of PDMS/IRMOF-3 coating SBSE-high performance liquid chromatography ultraviolet (HPLC-UV) detection was developed for the determination of seven target estrogens in environmental waters. Several parameters affecting extraction of seven target estrogens by SBSE (PDMS/IRMOF-3) including extraction time, stirring rate, pH, ionic strength, desorption solvent and desorption time were investigated. Under the optimal experimental conditions, the limits of detection (LODs, S/N=3) were found to be in the range of 0.15-0.35 μg/L. The linear range was 2-2,500 μg/L for 17α-ethynylestradiol and 1-2,500 μg/L for other estrogens. The relative standard deviations (RSDs) were in the range of 3.7-9.9% (n=8, c=20 μg/L) and the enrichment factors were from 30.3 to 55.6-fold (theoretical enrichment factor was 100-fold). The proposed method was successfully applied to the analysis of estrogens in environmental water samples, and quantitative recoveries were obtained for the spiking experiments.
在这项工作中，引入了三种金属有机骨架（MOFs），即 MOF-5、MOF-199 和 IRMOF-3，用于搅拌棒吸附萃取（SBSE）中，并通过溶胶-凝胶技术制备了新型聚二甲基硅氧烷（PDMS）/MOFs（包括 PDMS/MOF-5、PDMS/MOF-199 和 PDMS/IRMOF-3）涂层搅拌棒。对这些 PDMS/MOFs 涂层进行了表征，并对其进行了严格比较，以用于通过 SBSE 萃取七种目标雌激素（17-β-雌二醇、双烯雌酚、己烯雌酚、雌酮、4-t-辛基苯酚、双酚 A 和 17α-乙炔雌二醇），结果表明 PDMS/IRMOF-3 具有最高的萃取效率。基于上述事实，建立了一种 PDMS/IRMOF-3 涂层搅拌棒吸附萃取-高效液相色谱紫外检测（SBSE-HPLC-UV）新方法，用于测定环境水中的七种目标雌激素。考察了影响 SBSE（PDMS/IRMOF-3）萃取七种目标雌激素的几个参数，包括萃取时间、搅拌速率、pH 值、离子强度、洗脱溶剂和洗脱时间。在最佳实验条件下，发现七种目标雌激素的检测限（LODs，S/N=3）在 0.15-0.35 μg/L 范围内。17α-乙炔雌二醇的线性范围为 2-2500 μg/L，其他雌激素的线性范围为 1-2500 μg/L。相对标准偏差（RSDs）在 3.7-9.9%（n=8，c=20 μg/L）范围内，富集因子为 30.3-55.6 倍（理论富集因子为 100 倍）。该方法成功应用于环境水样中雌激素的分析，并对加标实验进行了定量回收。
